Diatomic phenols as nucleophilic components in the carbonylation of the chelated C,N-palladacycle of the ferrocene series

Article abstract of DOI:10.1007/s11172-005-0206-7

The carbonylation of the chelated palladium derivative of dimethylaminoferrocene in the presence of diatomic phenols affords mixtures of the corresponding mono- and diacylated dihydroxybenzenes containing a 2-dimethylaminomethylferrocenyl fragment in the acyl moiety.

Full text of DOI:10.1007/s11172-005-0206-7

2874
Russian Chemical Bulletin, International Edition, Vol. 53, No. 12, pp. 2874—2875, December, 2004
Diatomic phenols as nucleophilic components in the carbonylation
of the chelated C,Nꢀpalladacycle of the ferrocene series
T. V. Demeshchik,ꢀ L. L. Troitskaya, and V. I. Sokolov
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (095) 135 5085. Eꢀmail: stemos@ineos.ac.ru
The carbonylation of the chelated palladium derivative of dimethylaminoferrocene in the
presence of diatomic phenols affords mixtures of the corresponding monoꢀ and diacylated
dihydroxybenzenes containing a 2ꢀdimethylaminomethylferrocenyl fragment in the acyl moiety.
Key words: diatomic phenols, ferrocene derivatives, carbonylation, C,Nꢀpalladacycles.
The development of a strategy for the syntheses of
dimethylaminomethylferrocene (3a) and 1,2ꢀbis(2ꢀdimeꢀ
thylaminomethylꢀ1ꢀferrocenecarbonyloxy)benzene (4а).
In the case of resorcinol (2b), the carbonylation products
are 1ꢀ(3ꢀhydroxyphenoxycarbonyl)ꢀ2ꢀdimethylaminoꢀ
methylferrocene (3b) and 1,3ꢀbis(2ꢀdimethylaminoꢀ
methylꢀ1ꢀferrocenecarbonyloxy)benzene (4b). The carboꢀ
nylation in the presence of hydroquinone (2с) affords
1ꢀ(4ꢀhydroxyphenoxycarbonyl)ꢀ2ꢀdimethylaminomethylꢀ
ferrocene (3c) and 1,4ꢀbis(2ꢀdimethylaminomethylꢀ1ꢀ
ferrocenecarbonyloxy)benzene (4c). Their structures were
established by 1H NMR spectroscopy and mass spectromꢀ
etry (Table 1).
optically active ferroceneꢀbased dendrimers required to
study the behavior of polyatomic phenols as alcohol nuꢀ
cleophilic components in the carbonylation of chelated
palladacycles, affording metallic palladium and respective
esters. This reaction involving alkanols was repeatedly used
for the synthesis of planar chiral, including optically acꢀ
tive, 1,2ꢀderivatives of ferrocene.1—3 However, no inforꢀ
mation on the behavior of more acidic phenols in this
reaction was available. Therefore, in this work, we studied
the carbonylation of cyclopalladated dimethylaminoꢀ
methylferrocene (1) with isomeric dihydroxybenzenes,
viz., pyrocatechol (2a), resorcinol (2b), and hydroquinone
(2c), in a nonꢀhydroxylic solvent (Scheme 1). The choice
of these models was additionally favored by the fact that
the expected products can serve as polydentate ligands to
coordinate metal ions, because they contain two Nꢀ and
Оꢀdonors each and the πꢀdonating aryl group.
The upfield shift of one of the protons of the СН2
1
group in the H NMR spectrum of compound 3a and an
inverted chromatographic behavior (monosubstituted deꢀ
rivative 3a is eluted on SiO2 more rapidly than bisꢀderivaꢀ
tive 4a) are in the agreement with a strong hydrogen bond
of the free orthoꢀpositioned OH group.
The products of carbonylation of compound 1 with
pyrocatechol (2а) are 1ꢀ(2ꢀhydroxyphenoxycarbonyl)ꢀ2ꢀ
Since the bisꢀderivatives contain two planar chiral
ferrocenyl fragments, diastereomers can form, which exꢀ
Scheme 1
Substitution pattern
in the benzene ring
Yield (%)
Ratio
3 : 4
3
4
ortho (a)
meta (b)
para (с)
77
14
12
16
37
48
4.8 : 1
1 : 2.6
1 : 4
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2756—2758, December, 2004.
1066ꢀ5285/04/5312ꢀ2874 © 2004 Springer Science+Business Media, Inc.

Carbonylation of chelated palladacycle
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 12, December, 2004 2875
1
Table 1. Н NMR spectra, elemental analysis data, and mass spectrometry for the reaction products
Comꢀ
pound Calculated
Found
Molecular
formula
1H NMR, δ (J/Hz)
MS,
m/z
[M]+
(%)
N(CH3)2
CH2N
C5H5
C5H3
C6H4
C
H
N
3a
63.36 5.68 3.74 С20Н21FeNO3
63.34 5.58 3.69
2.15
(s, 6 Н)
2.86, 4.43
(AB system,
2 H, J = 12.0)
4.25
(s, 5 Н)
4.37, 4.40,
4.92
(all s,
6.82
(t, 1 Н);
6.94
379
3 H each)
(d, 1 Н);
7.07
(t, 1 Н);
7.26
(d, 1 Н)
6.41
(s, 1 Н);
6.59
3b
63.48 5.71 3.74 С20Н21FeNO3
63.34 5.58 3.69
2.25
(s, 6 Н)
3.29, 4.23
(AB system,
2 H, J = 12.47)
4.20
(s, 5 Н)
4.43, 4.52,
4.93 (all s,
3 H each)
379
(d, 2 Н);
7.07 (t, 1 Н)
6.89, 7.75
(both d,
2 H each)
7.29
3c
4a
68.01 6.19 3.48 С20Н21FeNO3• 2.30
3.35, 4.44
4.25
(s, 5 Н)
4.48, 4.54,
4.99 (all s,
3 H each)
4.33
(br.s, 2 Н);
4.49, 4.52,
379
648
68.28 5.95 3.06 •С6Н6
(s, 6 Н)
(AB system,
2 H, J = 12.76)
3.30 and 4.02,
3.36 and 4.02
(both AB
62.97 5.69 4.41 С34Н36Fe2N2O4 2.17,
4.12,
4.15
(both s,
62.99 5.60 4.32
2.20
(br.s, 4 Н)
(all s,
6 H each) system,
2 H each,
5 H each) 4.86, 4.90
(all s,
J = 12.1)
1 H each)
4b
4c
64.78 6.37 4.29 С34Н36Fe2N2O4• 2.22
3.28, 4.09
4.22
4.44, 4.53,
7.08
(d, 2 Н);
7.33
(s, 1 Н);
7.43
(t, 1 Н)
7.25
649
64.65 5.72 4.08 •0.5 С6Н6
(s, 12 Н) (AB system,
(s, 10 Н) 4.94 (all s,
6 H each)
[M + H]+
4 H, J = 12.64)
62.97 5.78 4.41 С34Н36Fe2N2O4 2.27
3.33, 4.14
4.26
4.48, 4.58,
648
62.99 5.60 4.32
(s, 12 Н) (AB system,
(s, 10 Н) 4.99 (all s,
6 H each)
(s, 4 Н)
4 H, J = 12.08)
plains the duplication of signals in the 1Н NMR spectra in
some cases.
as an eluent. The yields and ratios of the obtained products are
presented in Scheme 1. The elemental analysis data, mass specꢀ
tra, and 1Н NMR spectra are given in Table 1.
Experimental
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 02ꢀ03ꢀ
33355).
1
H NMR spectra were recorded on Bruker WPꢀ200 SY and
Bruker 400 HX instruments in CDCl3. Mass spectra (EI) were
obtained on a KratosꢀMSꢀ890 instrument. Solvents were puriꢀ
fied according to standard procedures.
References
A carbon monoxide flow was passed for 6 h through a susꢀ
pension of compound 1 (1.1 g, 1.45 mmol) and diatomic phenol
2a—c (0.16 g, 1.43 mmol) in a mixture of acetone (10 mL) and
benzene (50 mL). The reaction mixture was left to stay for ~14 h.
A precipitate was filtered off, washed with a CHCl3—Et3N (4 : 1)
mixture, and the liquid phase was concentrated by evaporation.
Benzene was added to the residue, and the resulting mixture was
treated with a saturated aqueous solution of Na2CO3. The orꢀ
ganic layer was separated, dried with MgSO4, and concentrated.
Chromatography was first carried out on a column with SiO2
and then on SiO2 plates, using benzene—Et3N (10 : 1) mixture
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J. Organomet. Chem., 1979, 182, 537.
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341 (in Russian).
Received July 23, 2004